EP2475698B1 - Mélange à base de liant et agent de revêtement ainsi que revêtements obtenus à partir de ce dernier, présentant une résistance élevée à la rayure, une grande stabilité aux intempéries et de bonnes propriétés optiques - Google Patents

Mélange à base de liant et agent de revêtement ainsi que revêtements obtenus à partir de ce dernier, présentant une résistance élevée à la rayure, une grande stabilité aux intempéries et de bonnes propriétés optiques Download PDF

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Publication number
EP2475698B1
EP2475698B1 EP20100744512 EP10744512A EP2475698B1 EP 2475698 B1 EP2475698 B1 EP 2475698B1 EP 20100744512 EP20100744512 EP 20100744512 EP 10744512 A EP10744512 A EP 10744512A EP 2475698 B1 EP2475698 B1 EP 2475698B1
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Prior art keywords
amine
blocked
hydroxyl
radicals
weight
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German (de)
English (en)
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EP2475698A1 (fr
Inventor
Günter Klein
Andreas Poppe
Sabine Holtschulte
Björn FELDMANN
Ulrike Wenking
Karl-Heinz Joost
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BASF Coatings GmbH
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BASF Coatings GmbH
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/40—High-molecular-weight compounds
    • C08G18/42—Polycondensates having carboxylic or carbonic ester groups in the main chain
    • C08G18/4288—Polycondensates having carboxylic or carbonic ester groups in the main chain modified by higher fatty oils or their acids or by resin acids
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/08—Processes
    • C08G18/16—Catalysts
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/08—Processes
    • C08G18/16—Catalysts
    • C08G18/166—Catalysts not provided for in the groups C08G18/18 - C08G18/26
    • C08G18/168—Organic compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/08—Processes
    • C08G18/16—Catalysts
    • C08G18/18—Catalysts containing secondary or tertiary amines or salts thereof
    • C08G18/1883—Catalysts containing secondary or tertiary amines or salts thereof having heteroatoms other than oxygen and nitrogen
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/2805—Compounds having only one group containing active hydrogen
    • C08G18/288—Compounds containing at least one heteroatom other than oxygen or nitrogen
    • C08G18/289—Compounds containing at least one heteroatom other than oxygen or nitrogen containing silicon
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
    • C08G18/71—Monoisocyanates or monoisothiocyanates
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
    • C08G18/71—Monoisocyanates or monoisothiocyanates
    • C08G18/718—Monoisocyanates or monoisothiocyanates containing silicon
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
    • C08G18/72—Polyisocyanates or polyisothiocyanates
    • C08G18/77—Polyisocyanates or polyisothiocyanates having heteroatoms in addition to the isocyanate or isothiocyanate nitrogen and oxygen or sulfur
    • C08G18/778—Polyisocyanates or polyisothiocyanates having heteroatoms in addition to the isocyanate or isothiocyanate nitrogen and oxygen or sulfur silicon
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
    • C08G18/72—Polyisocyanates or polyisothiocyanates
    • C08G18/80—Masked polyisocyanates
    • C08G18/8061—Masked polyisocyanates masked with compounds having only one group containing active hydrogen
    • C08G18/8083—Masked polyisocyanates masked with compounds having only one group containing active hydrogen with compounds containing at least one heteroatom other than oxygen or nitrogen
    • C08G18/809—Masked polyisocyanates masked with compounds having only one group containing active hydrogen with compounds containing at least one heteroatom other than oxygen or nitrogen containing silicon
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L75/00—Compositions of polyureas or polyurethanes; Compositions of derivatives of such polymers
    • C08L75/04—Polyurethanes
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D175/00—Coating compositions based on polyureas or polyurethanes; Coating compositions based on derivatives of such polymers
    • C09D175/04—Polyurethanes
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/08—Processes
    • C08G18/16—Catalysts
    • C08G18/18—Catalysts containing secondary or tertiary amines or salts thereof
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/40—High-molecular-weight compounds
    • C08G18/42—Polycondensates having carboxylic or carbonic ester groups in the main chain
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/31504—Composite [nonstructural laminate]
    • Y10T428/31652—Of asbestos
    • Y10T428/31663—As siloxane, silicone or silane

Definitions

  • the present invention relates to binder mixtures comprising at least one hydroxyl-containing compound (A) and at least 1.0 wt .-%, based on the non-volatile constituents of the mixture, at least one phosphorus- and nitrogen-containing catalyst (D) for the crosslinking of silane groups ,
  • the invention relates to coating compositions based on the binder mixture and multistage coating processes using these coating compositions and to the use of the coating compositions as a clearcoat or application of the coating process for automotive OEM finishing and automotive refinishing.
  • the EP-A-1 273 640 describes coating compositions comprising a polyol component and a crosslinking component consisting of aliphatic and / or cycloaliphatic polyisocyanates, wherein 0.1 to 95 mol% of the originally free isocyanate groups present are reacted with bisalkoxysilylamine.
  • these coating compositions contain conventional catalysts, such as organic tin compounds, for example dibutyltin dilaurate, amines or sulphonic acid-based catalysts, for example p-toluenesulphonic acid.
  • the in the EP-A-1 273 640 coating compositions described can be used for OEM series coating and have a good scratch resistance with good resistance to environmental influences. However, these coating compositions are particularly prone to postcrosslinking, since the conversion during thermal curing after application is insufficient. This has a negative effect on the weather stability in particular.
  • coating compositions which comprise at least one hydroxyl-containing compound (A) and at least one isocyanate-group-containing compound (B), one or more constituents of the coating agent having hydrolyzable silane groups.
  • catalyst (D) for the crosslinking of the silane groups contain phosphorus-containing catalysts, in particular amine-blocked phosphoric acid ethylhexyl partial esters.
  • amines with which the phosphoric acid esters are blocked there are mentioned tertiary amines, preferably triethylamine.
  • the coating compositions should be further improved in terms of optical properties, in particular in terms of Appearance.
  • these coating agents have only insufficient electrical resistance.
  • the electrical resistance of the coating materials is of particular importance.
  • the coating materials in the case of 2K coating compositions and the individual coating components, must not fall below a certain electrical resistance value.
  • the coating compositions or, in the case of 2K coating compositions, the individual coating components have an electrical resistance of at least 200 kOhm, preferably at least 250 kOhm and more preferably at least 350 kOhm.
  • the respective required limit values are system-specific limit values and can vary depending on the specific specifications of the system manufacturer. The The highest limits are therefore particularly preferred because they meet the specifications of different systems.
  • the electrical resistance is tested by means of an immersion measuring cell with a conductivity meter from the Byk Gardner type LC 2 according to DIN 55667 at 25 ° C.
  • the document DE10 2007 061 855 A1 relates to coating compositions based on aprotic solvents containing polyols and polyisocyanates with hydrolyzable silane groups, which lead to coatings having a high scratch resistance combined with high gloss and high weathering stability.
  • the table in paragraph [0109] discloses compositions containing a polyacrylate polyol, a partially silanized polyisocyanate, and a phosphorus-containing catalyst for crosslinking the silane groups. The phosphorus-containing catalyst is blocked with DBN.
  • Coating composition containing at least one hyperbranched, dendritic hydroxy-functional polyester (A) having an OH number ⁇ 180 mg KOH / g measured by DIN 53240, and polyisocyanates (B) containing at least partially hydrolyzable silane groups described.
  • catalyst (D) for the crosslinking of the silane groups phosphorus-containing catalysts, in particular amine-blocked phosphoric acid ethylhexyl partial esters, are used.
  • tertiary amines for example dimethyldodecylamine or triethylamine and bicyclic amines, such as.
  • diazabicyclononene (DBN), diazabicyclootan (DABCO), diazabicycloundecene (DBU) called.
  • DBN diazabicyclononene
  • DABCO diazabicyclootan
  • DBU diazabicycloundecene
  • Coating agents should therefore be made available which lead to a highly weather-resistant network and at the same time ensure high acid resistance.
  • the coating compositions should lead to coatings which are highly scratch-resistant even after the thermal curing and in particular have a high gloss retention after scratching.
  • the coatings and finishes, especially the clearcoats should also be able to be produced in layer thicknesses> 40 ⁇ m without stress cracks occurring. This is an essential prerequisite for the use of the coatings and coatings, in particular the clearcoats, in the technologically and aesthetically particularly demanding field of automotive OEM finishing.
  • the binder mixtures and the coating compositions prepared therefrom should not fall below a certain minimum value in terms of electrical resistance.
  • the electrical resistance of both the individual coating components, such as the binder mixture, and the coating compositions prepared therefrom is at least 200 kOhm, preferably at least 250 kOhm and particularly preferably at least 350 kOhm.
  • the coating compositions should also show good transparency (low haze values) and good flow, and lead to coatings with a good overall appearance.
  • the invention relates to coating compositions based on the binder mixture and multi-stage coating methods using these coating compositions and the use of the coating compositions as a clearcoat or application of the coating process for automotive OEM and automotive refinishing and for the coating of automotive attachments.
  • the binder mixtures according to the invention and the corresponding coating compositions according to the invention have an electrical resistance of at least 200 kOhm, preferably at least 250 kOhm and particularly preferably at least 350 kOhm, as in the field of automotive OEM finishing (OEM) required.
  • the coating compositions according to the invention provide novel coatings and coatings, especially clearcoats, which are highly scratch-resistant and, in contrast to common highly crosslinked scratch-resistant systems, are acid-resistant. Furthermore, the coatings and coatings according to the invention, especially the clearcoats, can also be produced in layer thicknesses> 40 ⁇ m without stress cracks occurring. Therefore, the coatings and coatings according to the invention, in particular the clearcoats, in the technological and aesthetically particularly demanding field of automotive OEM (OEM). They are characterized by a particularly high wash resistance and scratch resistance. In particular, the high scratch resistance of the coatings is given directly after the final curing of the coatings, so that the coatings can be handled easily following the final curing.
  • OEM automotive OEM
  • the binder mixtures and the coating compositions at the same time also show good transparency (low haze values) and good flow, and lead to coatings having a good overall optical impression.
  • the components according to the invention can be produced in a particularly simple and very reproducible manner and do not pose any significant toxicological and ecological problems in the paint application.
  • the binder mixtures according to the invention contain at least one hydroxy-functional polyester, wherein on average at least one hydroxyl function of the hydroxy-functional polyester is esterified with at least one acid selected from the group of isomeric C8-C9 monocarboxylic acids.
  • at least one acid selected from the group of isomeric C8-C9 monocarboxylic acids selected from the group of isomeric C8-C9 monocarboxylic acids.
  • the remainder of the isomeric C8-C9 monocarboxylic acid is saturated.
  • Such clearcoat compositions have good weathering stability.
  • the remainder of the C 8 -C 9 monocarboxylic acid is the radical of octanoic acid or isononanoic acid.
  • Isononanoic acid is particularly preferably used as the C8-C9 monocarboxylic acid.
  • hyperbranched, dendritic hydroxy-functional polyesters are preferably used.
  • Hyperbranched, dendritic compounds i. Hyperbranched, dendritic macromolecules and dendrimers can generally be described as three-dimensional, hyperbranched molecules with a tree-like structure. Dendrimers are highly symmetric, while similar macromolecules, termed hyperbranched and / or dendritic, may be asymmetric to a certain extent and yet retain the hyperbranched tree-like structure.
  • Hyperbranched and dendritic macromolecules can usually be prepared starting from an initiator or nucleus having one or more reactive sites and a number of branching layers ("generations") and optionally a layer of chain terminating molecules (divergent synthetic approach).
  • the continued replication of branching layers usually gives an increased branching multiplicity and optionally or, if desired, an increased number of end groups.
  • the layers are usually called generations and the branches dendrons.
  • the polyester (A) modified with an isomeric C8-C9 monocarboxylic acid used according to the invention preferably has a hydroxyl number of ⁇ 150 mg KOH / g, in particular a hydroxyl number of> 180 mg KOH / g, preferably 185-240 mg KOH / g according to DIN 53240.
  • polyesters which have a hydroxyl functionality (given by the number of free and esterified hydroxyl groups of the hydroxy-functional polyester) greater than 16.
  • Such clearcoat compositions have sufficient microhardness (ie> 90 N / mm 2, determined in accordance with DIN EN ISO 14577 with the aid of the Fischerscope measuring device from Fischer with a maximum force of 25.6 mN), are scratch-resistant and resistant to chemicals.
  • hydroxy-functional polyesters (A) which have an acid number ⁇ 8.0, preferably 0-6.0, determined in accordance with DIN 53402. Such acid numbers of the polyesters lead to a better compatibility of these polyesters with other coating raw materials and to an improved course.
  • hydroxy-functional polyesters (A) having a number average molecular weight of 1500-4000 g / mol, preferably 2000-3500 g / mol determined via GPC with a polystyrene standard in THF with 0.1 mol / l acetic acid.
  • A hydroxy-functional polyesters having a number average molecular weight of 1500-4000 g / mol, preferably 2000-3500 g / mol determined via GPC with a polystyrene standard in THF with 0.1 mol / l acetic acid.
  • polyesters having a polydispersity Mw / Mn ⁇ 4 are used. Particularly good properties result when the polyester has an even smaller polydispersity, i. Mw / Mn ⁇ 2.5, in particular Mw / Mn ⁇ 2.0.
  • the binder mixtures according to the invention and the corresponding coating compositions according to the invention may, in addition to the hydroxy-functional polyesters (A) essential to the invention, optionally contain further hydroxyl-containing compounds (C).
  • further hydroxyl-containing compounds (C) both low molecular weight polyols and oligomeric and / or polymeric polyols can be used.
  • component (C) of component (A) are various polyester polyols, polyurethane polyols, polysiloxane polyols and in particular polyacrylate polyols and / or polymethacrylate polyols and also their copolymers.
  • These optional compounds (C) are generally used in an amount of 0 to 30% by weight based on the total weight of the coating agent.
  • the binder mixtures according to the invention and the coating compositions according to the invention contain at least one phosphorus-containing and nitrogen-containing catalyst (D). It is also possible to use mixtures of two or more different catalysts (D).
  • Suitable catalysts (D) are amine-blocked substituted phosphonic diesters and amine-blocked diphosphonic diesters, preferably from the group consisting of amine-blocked acyclic phosphonic diesters, amine-blocked cyclic phosphonic diesters, amine-blocked acyclic diphosphonic diesters and amine-blocked cyclic diphosphonic diesters.
  • the corresponding unblocked phosphorus-containing catalysts are, for example, in the German patent application DE-A-102005045228 described.
  • amine-blocked substituted phosphoric acid monoesters and phosphoric diesters preferably from the group consisting of amine-blocked acyclic phosphoric diesters and amine-blocked cyclic phosphoric diesters. Blocking of the phosphorus-based catalysts with amines is necessary in order to be able to ensure the storage stability of the resulting formulations.
  • catalyst (D) particular preference is given to using amine-blocked phosphoric acid alkyl esters and phosphoric acid phenyl esters, very particularly preferably amine-blocked phosphoric acid phenyl esters.
  • catalysts based on phosphorus show particularly high molar conductivity in aqueous solutions, especially the anions, when they condense to higher phosphates (diphosphates, triphosphates and higher analogs), as in David R. Lide, CRC Handbook of Chemistry and Physics, 73rd Edition, 1992-93, pp. 5-112 , described.
  • R 1 is an acyclic aliphatic or araliphatic hydrocarbon radical having at least 3 C atoms.
  • R 2 is an identical or different from R 1 and / or R 3 acyclic aliphatic or araliphatic hydrocarbon radical.
  • R 1 , R 2 and R 3 may also contain aromatic structures in addition to purely aliphatic, acyclic structures.
  • R 3 is hydrogen or is equal to R 1 or is equal to R 2 or is one of R 1 and R 2 different acyclic aliphatic or araliphatic hydrocarbon radical.
  • R 3 may also contain aromatic structures in addition to purely aliphatic structures.
  • Tertiary amines of the formula (I) are preferably used, since these have the advantage that they can not react with the other constituents of the coating composition, in particular the isocyanate group-containing compounds (B).
  • Amines of the formula (I) are preferably used in which at least one of the radicals R 1 , R 2 and R 3 , preferably at least 2 of the radicals R 1 , R 2 and R 3 , aliphatic hydrocarbon radicals having 6 to 18 carbon atoms, especially preferably having 8 to 14 carbon atoms.
  • amines of the formula (I) are used in which at least one of the radicals R 1 , R 2 and R 3 is a branched aliphatic hydrocarbon radical is.
  • Particular preference is given to using amines of the formula (I) in which at least 2 of the radicals R 1 , R 2 and R 3 and preferably all 3 radicals R 1 , R 2 and R 3 are branched aliphatic hydrocarbon radicals.
  • amines of the formula (I) in which at least one, especially two, and very particularly preferably all of the radicals R 1 , R 2 and R 3 are branched aliphatic hydrocarbon radicals having at least 3 C atoms, preferably 6 to 18 C -Atomen, more preferably having 8 to 14 carbon atoms, are.
  • amines of the formula (I) in which at least one of the radicals R 1, R 2 and R 3 is a branched aliphatic hydrocarbon radical, it is possible to provide coating compositions which not only ensure the required electrical resistances but at the same time also crystallize the blocked one Avoid catalyst.
  • those amines of the formula (I) which lead to crystallization of the blocked catalyst. This is observed in particular for amines (I) in which either R 3 is hydrogen and R 1 and R 2 are linear aliphatic hydrocarbon radicals or all radicals R 1 , R 2 and R 3 are linear aliphatic hydrocarbon radicals. Then usually the addition of crystallization inhibitors is required to avoid precipitation of the blocked catalysts. However, the use or search for suitable crystallization inhibitors can prove difficult.
  • the catalyst (D) it is also possible according to the invention to block the catalyst (D) not only exclusively with an amine of the formula (I), but also to block the catalysts (D) used according to the invention, a mixture of 2 different amines (I) or a mixture of at least an amine of formula (I) with at least one different amine to use.
  • the use of suitable mixtures can also prevent a possible crystallization.
  • the branched amine (I) then acts as a crystallization inhibitor.
  • the amine-blocked phosphorus-containing catalyst (D) or the amine-blocked phosphorus-containing catalysts (D) particularly preferably contains at least one tertiary amine of the formula (I) with a contour length of more than 8 ⁇ m as blocking agent.
  • the contour length is estimated by projecting the respective amine in its entire extent, taking into account the respective hydrides of the individual atoms and the consequent bond angles in a plane. This projection, in turn, is used to project the maximum extent of each molecule onto a line. By way of example, this should be shown by the estimation of the contour length of the pentylamine.
  • binding Bond length [pm] Number alpha Projected length [pm] Contribution to the contour length [pm] C - C 154 4 30 ° 134 536 C - H 110 1 30 ° 95.3 95.3 N - C 101 1 30 ° 86.6 86.6
  • the bond lengths are taken from the literature, see, for. B. Marye A. Fox, James K. Whitesell: Organic Chemistry. Spektrum Akademischer Verlag, 1995, ISBN 3860252496 ,
  • the total contour length results from the sum of the individual contributions according to the table.
  • suitable amines (I) with which the phosphoric acid esters are blocked are linear aliphatic amines such as trioctylamine, dioctylamine, octyldimethylamine, dinonylamine, trinonylamine, nonyldimethylamine, tridodecylamine, dodecyldimethylamine, and the like. to call.
  • branched amines such as di (isopropanol) amine, diisoamylamine, diisobutylamine, diisononylamine and in particular branched tertiary Amines, for example, isododecyl-dimethyl-amine, tris (2-ethylhexyl) amine, triisoamylamine, triisononylamine, triisooctylamine and triisopropylamine, optionally together with linear aliphatic amines used.
  • catalyst (D) amine-blocked Phosphortica Tartyl
  • catalyst (D) amine-blocked Phosphortica Tartylester and here in particular with tris (2-ethylhexyl) amine, dodecyldimethylamine and / or isododecyldimethylamine, most preferably with tris (2-ethylhexyl) amine-blocked Phosphorklaphenylester used.
  • Certain amine-blocked phosphoric acid catalysts are also commercially available (e.g., Nacure types from King Industries).
  • the catalysts are preferably in proportions of at least 1.0 wt .-%, preferably in proportions of 2.0 to 7.0 wt .-% and particularly preferably in proportions of 2.0 to 5.0 wt .-%, based to the non-volatile constituents of the binder mixture according to the invention used.
  • a lower efficiency of the catalyst can be partially compensated by correspondingly higher amounts.
  • the highest possible concentration of the blocked catalyst should be aimed for.
  • This has the advantage that the crosslinking of the silane groups as completely as possible happens and thus a high network density, consequently a high scratch resistance and good chemical resistance can be achieved.
  • the risk of post-crosslinking processes is particularly low if a quasi-complete conversion of the silane groups is achieved directly after the end of the curing process.
  • the upper limit with respect to the amount of catalyst to be used is given by the electrical resistance, which may vary depending on the specifications of the equipment manufacturer.
  • the binder mixtures according to the invention and / or the coating compositions according to the invention may also contain a further amine catalyst based on a bicyclic amine, in particular an unsaturated bicyclic amine.
  • suitable amine catalysts are 1,5-diazabicyclo [4.3.0] non-5-ene or 1,8-diazabicyclo [5.4.0] undec-7-ene.
  • These amine catalysts are preferably used in proportions of from 0.01 to 20% by weight, particularly preferably in proportions of from 0.1 to 10% by weight, based on the nonvolatile constituents of the binder mixture according to the invention.
  • the binder mixture usually also contains at least one organic solvent.
  • Suitable solvents for the binder mixture according to the invention are, in particular, those which are chemically inert in the binder mixture and in the coating agent in relation to the compounds (A), (B) and, if appropriate, (C) and which also do not react with (A) during the curing of the coating agent. and (B) react.
  • solvents examples include aliphatic and / or aromatic hydrocarbons such as toluene, xylene, solvent naphtha, Solvesso 100 or Hydrosol® (ARAL), ketones such as acetone, methyl ethyl ketone or methyl amyl ketone, esters such as ethyl acetate, butyl acetate, pentyl acetate or ethyl ethoxypropionate, ethers or mixtures of the abovementioned solvents.
  • the aprotic solvents or solvent mixtures preferably have a water content of not more than 1% by weight, more preferably not more than 0.5% by weight, based on the solvent.
  • butyl acetate as a solvent, particularly preferably at least 60 wt .-% butyl acetate, based on the total weight of the solvent mixture used.
  • Other solvents are used to adjust the corresponding desired evaporation rates.
  • the solids content of the binder mixture according to the invention is advantageously at least 50% by weight, preferably at least 70% by weight.
  • binder mixture according to the invention may contain one or more of the customary and known paint additives (F) described below.
  • the coating compositions according to the invention contain, in addition to the binder mixture according to the invention described above, at least one saturated compound (B) with isocyanate groups which contains at least partially hydrolyzable silane groups.
  • the di- and / or polyisocyanates which are used as base for the isocyanate-containing compounds (B) preferably used according to the invention are preferably saturated or unsubstituted aromatic, aliphatic, cycloaliphatic and / or heterocyclic polyisocyanates which are known per se.
  • polyisocyanates examples include: 2,4-toluene diisocyanate, 2,6-toluene diisocyanate, diphenylmethane-4,4'-diisocyanate, diphenylmethane-2,4'-diisocyanate, p-phenylene diisocyanate, biphenyl diisocyanates, 3,3'-dimethyl-4 , 4'-diphenylene diisocyanate, tetramethylene-1,4-diisocyanate, hexamethylene-1,6-diisocyanate, 2,2,4-trimethylhexane-1,6-diisocyanate, isophorone diisocyanate, ethylene diisocyanate, 1,12-dodecane diisocyanate, cyclobutane-1, 3-diisocyanate, cyclohexane-1,3-diisocyanate, cyclohexane-1,4-diis
  • Particularly preferred polyisocyanates PI are hexamethylene-1,6-diisocyanate, isophorone diisocyanate and 4,4'-methylenedicyclohexyl diisocyanate, their biuret dimers and / or isocyanurate trimers.
  • the polyisocyanates are polyisocyanate prepolymers having urethane structural units which are obtained by reacting polyols with a stoichiometric excess of the aforementioned polyisocyanates.
  • Such polyisocyanate prepolymers are, for example, in US-A-4, 598,131 described.
  • the isocyanate group-containing compound (B) contains at least partially hydrolyzable silane groups. These hydrolyzable silane groups lead to the formation of the Si-O-Si network, which is statistically distributed in the final cured coating. This means that there is no specific enrichment or depletion of the Si-O-Si network in certain areas of the coating.
  • the respective preferred alkoxy radicals (OR ') may be identical or different, but it is crucial for the structure of the radicals how they influence the reactivity of the hydrolyzable silane groups.
  • R ' is preferably an alkyl radical, in particular having 1 to 6 C atoms. Particularly preferred are R 'radicals which increase the reactivity of the silane groups, i. represent good leaving groups. In this respect, a methoxy radical is preferred over an ethoxy radical and this in turn is preferred over a propoxy radical. Therefore, R 'is preferably ethyl and / or methyl, in particular methyl.
  • organofunctional silanes can also be significantly affected by the length of the spacers X between silane functionality and organic functional group which serves to react with the modifying constituent.
  • examples include the "alpha" - called silanes, which are available from the company Wacker, and in which a methylene group is in place of the present in "gamma” silanes propylene group between Si atom and functional group.
  • the invention particularly preferred with the structural units (III) and (IV) functionalized isocyanate compounds (B) are particularly preferably by reacting the aforementioned di- and / or polyisocyanates with a compound of formula (IIIa) HN (X-SiR "x (OR ') 3-x) n (X'-SiR” y (OR') 3-y) m (IIIa), and a compound of formula (IVa) HZ- (X-SiR "x (OR ') 3-x) (IVa), obtained, wherein the substituents have the abovementioned meaning.
  • Preferred compounds (IIIa) according to the invention are bis (2-ethyltrimethoxysilyl) amine, bis (3-propyltrimethoxysilyl) amine, bis (4-butyltrimethoxysilyl) amine, bis (2-ethyltriethoxysilyl) amine, bis (3-propyltriethoxysilyl) amine and / or amine bis (4-butyltriethoxysilyl).
  • Very particular preference is given to bis (3-propyltrimethoxysilyl) amine.
  • Such aminosilanes are available, for example, under the trade name DYNASYLAN® from DEGUSSA or Silquest® from OSI.
  • Preferred compounds (IVa) according to the invention are aminoalkyltrialkoxysilanes, such as preferably 2-aminoethyltrimethoxysilane, 2-aminoethyltriethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 4-aminobutyltrimethoxysilane, 4-aminobutyltriethoxysilane.
  • Particularly preferred compounds (IVa) are N- (2- (trimethoxysilyl) ethyl) alkylamines, N- (3- (trimethoxysilyl) propyl) alkylamines, N- (4- (trimethoxysilyl) butyl) alkylamines, N- (2- (triethoxysilyl ) ethyl) alkylamines, N- (3- (triethoxysilyl) propyl) -alkylamines and / or N- (4- (triethoxysilyl) butyl) alkylamines.
  • Very particularly preferred is N- (3- (trimethoxysilyl) propyl) butylamine.
  • Such aminosilanes are available, for example, under the trade name DYNASYLAN® from DEGUSSA or Silquest® from OSI.
  • the present invention particularly preferred with the structural units (III) and (IV) functionalized isocyanate compounds (B) are particularly preferably prepared by reacting the aforementioned di- and / or polyisocyanates with the aforementioned compounds (IIIa) and (IVa) by between 2.5 and 90 mol%, preferably 5 to 85 mol%, particularly preferably 7.5 to 80 mol%, of the isocyanate groups in the polyisocyanate parent with at least one compound (IIIa) and from 2.5 to 90 mol%, preferably from 5 to 85 mol%, particularly preferably from 7.5 to 80 mol%, of the isocyanate groups in the polyisocyanate main body with at least one compound (IVa) be implemented.
  • the total amount of the isocyanate groups reacted with the compounds (IIIa) and (IVa) in the polyisocyanate compound (B) is between 5 and 95 mol%, preferably between 10 and 90 mol%, more preferably between 15 and 85 mol% of the isocyanate groups in the polyisocyanate parent.
  • Very particularly preferred isocyanate group-containing compounds (B) are reaction products of hexamethylene-1,6-diisocyanate and / or isophorone diisocyanate, and / or their isocyanurate trimers with bis (3-propyltrimethoxysilyl) amine and N- (3- (trimethoxysilyl) propyl) butylamine ,
  • the solids content of the polyisocyanate hardener (B) used according to the invention is advantageously at least 50% by weight, preferably at least 70% by weight.
  • the polyisocyanate curing agent used according to the invention preferably comprises at least one water scavenger, for example reactive silanes having a higher reactivity with respect to water than isocyanates.
  • water scavengers OrthoameisenLiteretrialkylester.
  • Triethyl orthoformate is particularly preferably used as the water scavenger.
  • from 0.01% to 10%, preferably from 0.03% to 5.0%, by weight of at least one water scavenger based on the total non-volatile content of the coating agent is added.
  • the reaction of the isocyanate-containing compounds (B) with the compounds (IIIa) and (IVa) is preferably carried out in an inert gas atmosphere at temperatures of at most 100 ° C., preferably of not more than 60 ° C.
  • the reaction of the isocyanate group-containing compounds (B) with the compounds (IIIa) and (IVa) is preferably carried out in a solvent or in a solvent mixture in the presence of at least one water scavenger and in the presence of at least one amine, preferably in the presence of at least one tertiary amine, such as, for example 1 , 4-diazabicyclo [2.2.2] octane (DABCO), triethylamine and diisopropylethylamine, especially triethylamine.
  • DABCO 4-diazabicyclo [2.2.2] octane
  • At least 1% by weight, preferably at least 2% by weight, particularly preferably at least 3% by weight and very preferably at least 4% by weight of at least one water scavenger, preferably triethyl orthoformate, are preferred during the synthesis, based on the total content of Reaction mixture of non-volatile components added.
  • the amine is preferably used during the synthesis in an amount of from 2 to 6% by weight, based on the total content of the reaction mixture of non-volatile constituents.
  • Triethylamine is particularly preferably used during the synthesis in an amount of 1.5 to 3.5 wt .-%, based on the total content of the reaction mixture of nonvolatile fractions.
  • the solvent or solvent mixture in which the polyisocyanate hardeners are prepared may consist of aromatic hydrocarbons such as 1,2,4-trimethylbenzene, mesitylene, xylene, propylbenzene and isopropylbenzene.
  • aromatic hydrocarbons such as 1,2,4-trimethylbenzene, mesitylene, xylene, propylbenzene and isopropylbenzene.
  • An example of a suitable solvent mixture of aromatic hydrocarbons is solvent naphtha.
  • the solvent in which the polyisocyanate hardeners are prepared can also consist of aliphatic hydrocarbons, ketones, such as acetone, methyl ethyl ketone or methyl amyl ketone, esters, such as ethyl acetate, butyl acetate, pentyl acetate or ethyl ethoxypropionate, ethers or mixtures of the abovementioned solvents, solvent mixtures having a high Percentage of butyl acetate, in particular at least 60 wt .-% butyl acetate, based on the total weight of the solvent mixture, are preferred.
  • the solvent mixture particularly preferably contains at least 80% by weight of butyl acetate, in particular at least 95% by weight of butyl acetate. Very particularly advantageous is worked in pure butyl acetate.
  • the polyisocyanate curing agent may also preferably be prepared by virtue of the fact that, in a first step, on average, per molecule, at most one of the isocyanate groups of the polyisocyanate and the amino-functional one Alkoxysilane is reacted and in a second step, the resulting intermediate is converted by dimerization, trimerization, urethane, biuret or allophanate formation to form a polyisocyanate.
  • the free isocyanate groups of the isocyanate-containing compounds B can also be used in blocked form. This is preferably the case when the coating compositions according to the invention are used as one-component systems.
  • blocking it is possible in principle to use any blocking agent which can be used for blocking polyisocyanates with a sufficiently low deblocking temperature.
  • blocking agents are well known to those skilled in the art. Preference is given to blocking agents as described in US Pat EP-A-0 626 888 and EP-A-0 692 007 are used.
  • the proportion by weight of the hydroxyl-containing polyesters (A) to be used, based on the weight fraction of the isocyanate-containing compounds (B), depends on the hydroxyl equivalent weight of the polyester and on the equivalent weight of the free isocyanate groups of the polyisocyanate.
  • the coating composition according to the invention are preferably 2.5 to 97.5 mol%, based on the sum of the structural units (III) and (IV), of structural units (III) and 2.5 to 97.5 mol%, based on the Sum of the structural units (III) and (IV), of structural units (IV) present.
  • the coating compositions according to the invention preferably contain between 2.5 and 97.5% by weight, particularly preferably between 5 and 95% by weight, very particularly preferably between 10 and 90% by weight, in particular between 20 and 80% by weight. , based on the content of non-volatile substances in the coating composition of the hydroxyl-containing polyester (A) and preferably between 2.5 and 97.5 wt .-%, particularly preferably between 5 and 95 wt .-%, most preferably between 10 and 90 wt .-%, in particular between 20 and 80 wt .-%, based on the content of nonvolatile substances in the coating agent, the isocyanate compounds (B).
  • the structural elements (III) and (IV) are preferably in proportions from 2.5 to 97.5 mol%, more preferably between 5 and 95 mol%, and most preferably between 10 and 90 mol%.
  • the content of structural units (III) and / or (IV) is also preferred to select the content of structural units (III) and / or (IV) to a maximum in that the coating compositions of the invention comprise less than 6.5% by mass of Si of the structural units (III) and / or (IV), very particularly not more than 6.0% by mass of the structural units (III) and / or (IV) on the solids content of the coating compositions.
  • the silane content in mass% Si is determined by calculation from the amounts used in the compounds (IIIa) and (IVa).
  • the proportions by weight of the polyester (A), the compound (C) optionally used and the polyisocyanate (B) are preferably chosen such that the molar equivalent ratio of the unreacted Isocyanate groups of the isocyanate compounds (B) to the hydroxyl groups of the polyester (A) and optionally used compound (C) between 0.9: 1.0 and 1.2: 1.0, preferably between 0.95: 1.0 and 1.1: 1.0 is more preferably between 0.98: 1.0 and 1.05: 1.0.
  • the isocyanate group-containing compounds (B) are selected whose free isocyanate groups are blocked with the blocking agents described above.
  • the binder mixture comprising the hydroxyl-containing polyester (A), if appropriate (C), the catalyst (D), a part of the solvent and optionally further below components described, with a further coating component, containing the isocyanate group-containing compound (B) and optionally further of the components described below mixed in a conventional manner.
  • Suitable solvents for the coating compositions of the invention are, in particular, those which are chemically inert in the coating composition compared to the compounds (A), (B) and, if appropriate, (C) and which also do not react with (A) and (B) during the curing of the coating composition. react.
  • solvents examples include aliphatic and / or aromatic hydrocarbons such as toluene, xylene, solvent naphtha, Solvesso 100 or Hydrosol® (ARAL), ketones such as acetone, methyl ethyl ketone or methyl amyl ketone, esters such as ethyl acetate, butyl acetate, pentyl acetate or ethyl ethoxypropionate, ethers or mixtures of the abovementioned solvents.
  • the aprotic solvents or solvent mixtures preferably have a water content of not more than 1% by weight, more preferably not more than 0.5% by weight, based on the solvent.
  • butyl acetate as solvent more preferably at least 60 wt .-% butyl acetate, based on the total weight of the solvent mixture used.
  • Other solvents are used to adjust the corresponding desired evaporation rates.
  • binders (E) which are preferably combined with the hydroxyl groups of the polyester (A) and / or with the free isocyanate groups of the compound (B) and / or the alkoxysilyl groups of the compounds (B) and / or (C) and can form network points.
  • component (E) aminoplast resins and / or epoxy resins usable. Suitable are the customary and known amino resins whose methylol and / or methoxymethyl groups may be partially defunctionalized by means of carbamate or allophanate groups.
  • Crosslinking agents of this type are described in the patents US-A-4,710,542 and EP-B-0 245 700 as well as in the article by B. Singh and coworkers "Carbamylmethylated Melamines, Novel Crosslinkers for the Coatings Industry" in Advanced Organic Coatings Science and Technology Series, 1991, Volume 13, pages 193 to 207 , described.
  • such components (E) are used in proportions of up to 40% by weight, preferably of up to 30% by weight, particularly preferably of up to 25% by weight, based on the nonvolatile constituents of the coating composition ,
  • the binder mixture according to the invention or the coating composition according to the invention at least one conventional and known paint additive (F) in effective amounts, ie in amounts preferably up to 30 wt .-%, particularly preferably up to 25 wt .-% and in particular up to 20 Wt .-%, each based on the nonvolatile constituents of the coating composition.
  • F paint additive
  • light stabilizers based on sterically hindered amines (HALS), light stabilizers based on UV absorbers, such as benzotriazoles or oxalanilides, as well as rheological aids can also unfavorably influence the electrical resistance of the coating component or the coating composition containing them, ie lower them so that their amounts are not should be chosen too high.
  • these additives are also preferably used in certain minimum amounts in order to ensure the desired mechanical and technological properties of the coating compositions or coatings.
  • the amounts used can be easily determined by the person skilled in the art on the basis of less routine tests.
  • binder mixtures or coating compositions which contain at least one light stabilizer based on sterically hindered amines (HALS), particular preference being given to binder mixtures or coating compositions which contain at least one light stabilizer based on sterically hindered amines (HALS) in a concentration of more than 0 , 5 wt.% To a maximum of 3.0 wt .-%, each based on the non-volatile constituents of the coating composition.
  • HALS sterically hindered amines
  • binder mixtures or coating compositions which comprise at least one UV absorber
  • binder mixtures or coating compositions being particularly preferred which comprise at least one UV absorber in a concentration of more than 0.5% by weight to a maximum of 3.0% by weight. %, in each case based on the nonvolatile constituents of the coating composition.
  • binder mixtures or coating compositions which contain at least one light stabilizer based on sterically hindered amines (HALS) and at least one UV absorber.
  • HALS sterically hindered amines
  • binder mixtures or coating compositions containing at least one rheology aid are also preferred, more preferably in a concentration of more than 2 wt.% To a maximum of 10 wt .-%, each based on the non-volatile constituents of the coating composition.
  • the binder mixture according to the invention or the coating composition of the invention may contain further pigments and / or fillers and serve to produce pigmented topcoats.
  • the pigments and / or fillers used for this purpose are known to the person skilled in the art.
  • the coatings prepared according to the invention from the coating compositions according to the invention also adhere well to already cured electrodeposition coatings, surfacer finishes, basecoats or customary and known clearcoats, they are excellently suitable for automotive refinish or modular scratch-resistant equipment of already lacquered in addition to use in automotive OEM (OEM) paint automobile bodies.
  • the application of the coating compositions according to the invention can be carried out by all customary application methods, such as, for example, spraying, knife coating, brushing, pouring, dipping, impregnating, trickling or rolling.
  • the substrate to be coated can rest as such, with the application device or system being moved.
  • the substrate to be coated in particular a coil, can also be moved, with the application system rests relative to the substrate or is moved in a suitable manner.
  • spray application methods such as compressed air spraying, airless spraying, high rotation, electrostatic spray application (ESTA), optionally combined with hot spray application such as hot air hot spraying.
  • ESA electrostatic spray application
  • the curing of the applied coating compositions according to the invention can take place after a certain rest period.
  • the rest period serves, for example, for the course and degassing of the paint layers or for the evaporation of volatile components such as solvents.
  • the rest period can be supported and / or shortened by the application of elevated temperatures and / or by a reduced air humidity, provided that no damage or changes in the paint layers occur, such as premature complete crosslinking.
  • the thermal curing of the coating compositions has no special features, but is carried out by the usual and known methods such as heating in a convection oven or irradiation with IR lamps. Here, the thermal curing can also be done gradually.
  • Another preferred curing method is near infrared (NIR) curing.
  • the thermal curing is carried out at a temperature of 30 to 200 ° C, more preferably 40 to 190 ° C and in particular 50 to 180 ° C for a time of 1 min to 10 h, more preferably 2 min to 5 h and in particular 3 min to 3 h, wherein at the temperatures used for automotive refinishing, which are preferably between 30 and 90 ° C, longer curing times can be used.
  • the coating compositions according to the invention provide new cured coatings, in particular coatings, especially clearcoats, moldings, especially optical moldings, and self-supporting films which are highly scratch-resistant and in particular resistant to chemicals and weathering and have a very good overall visual impression.
  • the coatings and coatings according to the invention, especially the clearcoats can also be produced in layer thicknesses> 40 ⁇ m without stress cracks occurring.
  • the coating compositions according to the invention are therefore outstandingly suitable as decorative, protective and / or effective, highly scratch-resistant coatings and finishes of bodies of vehicles (especially motor vehicles, such as motorcycles, buses, trucks or cars) or parts thereof; of buildings in the interior and exterior; of furniture, windows and doors; of plastic moldings, in particular CDs and windows; of industrial small parts, of coils, containers and packaging; of white goods; of films; of optical, electrotechnical and mechanical components as well as glass hollow bodies and everyday objects.
  • bodies of vehicles especially motor vehicles, such as motorcycles, buses, trucks or cars
  • parts thereof of buildings in the interior and exterior
  • furniture, windows and doors of plastic moldings, in particular CDs and windows
  • of industrial small parts, of coils, containers and packaging of white goods
  • of films of optical, electrotechnical and mechanical components as well as glass hollow bodies and everyday objects.
  • the coating compositions and coatings according to the invention are used in the technologically and aesthetically particularly demanding field of automotive OEM finishing and automotive refinishing.
  • the coating compositions of the invention are particularly preferably used in multistage coating processes, in particular in processes in which a pigmented basecoat film is applied to an optionally precoated substrate, followed by a coating with the coating composition of the invention.
  • the invention therefore also provides effect and / or coloring multicoat paint systems comprising at least one pigmented basecoat film and at least one clearcoat film disposed thereon characterized in that the clearcoat film has been prepared from the coating composition of the invention.
  • Both waterborne basecoats and basecoats based on organic solvents can be used. Suitable basecoats are for example in the EP-A-0 692 007 and in the documents cited in column 3, lines 50ff.
  • the applied basecoat is first dried, that is, the basecoat film is removed in an evaporation phase, at least a portion of the organic solvent or of the water. The drying is preferably carried out at temperatures from room temperature to 80 ° C. After drying, the coating composition according to the invention is applied.
  • the two-coat coating is preferably under conditions used in automotive OEM finishing at temperatures of 30 to 200 ° C, more preferably 40 to 190 ° C and especially 50 to 180 ° C, for a time of 1 min to 10 h, more preferably 2 min up to 5 hours and especially 3 minutes to 3 hours, wherein longer curing times may also be used for the automotive refinish temperatures, which are preferably between 30 and 90 ° C.
  • the layers produced with the coating composition according to the invention are distinguished, above all, by a particularly high resistance to chemicals and weathering, as well as a very good resistance to scrubbing and scratching, and at the same time show a very good overall appearance (very good appearance).
  • the coating composition of the invention is used as a transparent clearcoat for coating plastic substrates, in particular transparent plastic substrates.
  • the coating agents include UV absorbers, which in quantity and type also on the effective UV protection of the plastic substrate are designed.
  • the coating compositions are characterized by an outstanding combination of scratch resistance and weathering stability combined with very good appearance.
  • the thus coated plastic substrates are preferably used for the replacement of glass components in the automotive industry, wherein the plastic substrates are preferably made of polymethyl methacrylate or polycarbonate.
  • the reaction mixture is stirred at 200 ° C until an acid number of less than 5 mg KOH / g (determined according to DIN 53402) is reached.
  • the mixture is cooled to 145 ° C and dissolved in 840 parts by weight of butyl acetate.
  • the resulting polyester resin has a solids content of 78.8 wt .-%.
  • the resulting hydroxyl number is 190 mg KOH / g (determined according to DIN 53240), the acid number is 5.8 mg KOH / g (DIN 53402).
  • the solution thus obtained was initially storage-stable. After 4 weeks, however, the material crystallized out and could be used as a pure substance only after a short warming to 60 ° C and complete dissolution of the crystals.
  • a 5 l Juvo reaction vessel with heating mantle, thermometer, stirrer and with attached condenser was charged with 875.7 g of an aromatic solvent. While stirring and inert gas atmosphere (200 cm3 / min nitrogen), the aromatic solvent was heated to 160 ° C under overpressure (max 3.5 bar). Using a metering pump, a mixture of 37.5 g of di-tert-butyl peroxide and 138.6 g of an aromatic solvent was added uniformly and dropwise over 4.75 hours.
  • the resulting resin had an acid number of 15 mg KOH / g (according to DIN 53402), a solids content of 65% +/- 1 (60 min, 130 ° C) and a viscosity of 8.5 dPa * s according to the test procedure according to DIN ISO 2884-1 (55% in solvent naphtha).
  • a 1 liter reactor was charged with 423.5 g of the resin solution and diluted with 29.4 g of butyl acetate. Thereafter, 11.2 g of benzylamine were added and the mixture was stirred for 30 minutes. After this time, a mixture of 8.8 g of hexamethylene diisocyanate and 17.1 g of butyl acetate was added so that a reaction temperature of 40 ° C was not exceeded at the expense of high shear forces.
  • the mixture thus obtained had a viscosity of> 800 mPas (10 s -1) (Z3) (DIN ISO 2884-1) and a solids content of 59.0% (60 min, 130 ° C).
  • trimerized hexamethylene diisocyanate commercial product Basonat HI 100 from BASF SE, Ludwigshafen
  • 36.093 parts by weight of butyl acetate and 2.458 parts by weight of triethyl orthoformate 36.296 parts by weight of trimerized hexamethylene diisocyanate (commercial product Basonat HI 100 from BASF SE, Ludwigshafen)
  • 36.093 parts by weight of butyl acetate 36.093 parts by weight of butyl acetate and 2.458 parts by weight of triethyl orthoformate.
  • the binder mixtures of Examples 1 to 4 and the binder mixtures of Comparative Examples 1 to 4 were prepared from the components listed in Table 1 by mixing.
  • Table 1 Composition of the binder mixtures in parts by weightprojects.-Ex.1uploadss.-Ex.2uploadss.-EX3fects.-Ex.
  • Dynoadd F1 commercial leveling additive from DYNEA ASA 2
  • Tinuvin® 384 commercial light stabilizer based on a benzotriazole Ciba 3
  • Tinuvin® 152 commercial light stabilizer based on a sterically hindered amine from Ciba 4) 30% solution of DBN diazabicyclononene) in butanol 5) isotridecyl alcohol
  • the coating compositions of Examples 2 to 4 and V1 to V4 prepared using the binder mixtures of Examples 2 to 4 and those prepared using the binder mixtures of Comparative Examples C1 to V4 were examined for their scratch resistance.
  • To prepare the coating compositions in each case 100 parts by weight of the binder mixtures were mixed and homogenized with the parts by weight of the partially silanized isocyanate B 1 shown in FIG. Table 3: Composition of the coating compositions of Comparative Examples V1 to V4 and the coating compositions of Examples 2 to 4 according to the invention in parts by weight See V1 See V2 See V3 See V4 Ex.
  • Example 3 Example 4 Binder mixture V1 100 Binder mixture V2 100 Binder mixture V3 100 Binder mixture V4 100 Binder mixture B2 100 Binder mixture B3 100 Binder mixture B4 100 Isocyanate hardener B1 123.7 123.0 122.3 121.6 122.3 121.6 120.9
  • the coating compositions were applied shortly after homogenization in three spray passes at 2.5 bar pneumatically on a commercial water-based paint black uni BASF Coatings AG. Thereafter, the respective resulting coating is flashed for 5 minutes at room temperature and then baked at 135 ° C for 20 minutes.
  • the binder mixtures of Comparative Examples V5 to V8 are prepared from the components indicated in Table 5.
  • Table 5 Composition of the binder mixtures of Comparative Examples V5 to V8 in parts by weight See V5 See V6 See V7 See V8 Polyester A1 36.6 36.6 36.6 36.6 Additive F1 21.0 21.0 21.0 21.0 butyl 14.7 14.7 14.7 14.7 Butylglykoldiacetat 2.1 2.1 2.1 2.1 triethylorthoformate 2.1 2.1 2.1 2.1 Dynoadd 1) 0.20 0.20 0.20 0.20 Tin.384 2) 1.60 1.60 1.60 1.60 Tin.152 3) 2.75 2.75 2.75 2.75 Cat.
  • Dynoadd F1 commercial leveling additive from DYNEA ASA 2
  • Tinuvin® 384 commercial light stabilizer based on a benzotriazole Ciba 3
  • Tinuvin® 152 commercial light stabilizer based on a sterically hindered amine from Ciba 4) 30% solution of DBN diazabicyclononene) in butanol 5) isotridecyl alcohol
  • V hydr ⁇ (r Kontour / 2) 3 A corresponding estimation of the contour lengths and the resulting hydrodynamic volumes is shown in Table 7 below and is based on the assumption an average bond length of 155 pm and a projected bond angle of 30 °.
  • Table 7 A corresponding estimation of the contour lengths and the resulting hydrodynamic volumes is shown in Table 7 below and is based on the assumption an average bond length of 155 pm and a projected bond angle of 30 °.
  • the binder mixtures of Inventive Examples 5 to 10 are prepared from the components specified in Table 8.
  • Table 8 Composition of the binder mixtures in parts by weight Example 5
  • Example 6 Example 7 Ex. 8 Ex. 9 Ex.
  • Dynoadd F1 commercial leveling additive from DYNEA ASA 2
  • Tinuvin® 384 commercial light stabilizer based on a benzotriazole Ciba 3
  • Tinuvin® 152 commercial light stabilizer based on a sterically hindered amine from Ciba 4) 30% solution of DBN diazabicyclononene) in butanol 5) isotridecyl alcohol
  • the binder mixtures of Examples 7 to 10 tend to crystallize the catalyst, so that preferably a crystallization inhibitor is added. It is also possible to block the catalyst with a mixture of dodecyldimethylamine and isododecyldimethylamine.

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Claims (15)

  1. Mélange de liant à base de solvants aprotiques, contenant
    au moins un composé (A) contenant des groupes hydroxyle et
    au moins 1,0% en poids, par rapport aux constituants non volatils du mélange, d'au moins un catalyseur (D) contenant du phosphore et de l'azote pour la réticulation des groupes silanes, caractérisé en ce que le mélange contient
    (i) comme composé (A) contenant des groupes hydroxyle, au moins un polyester (A) à fonctionnalité hydroxy, dans lequel en moyenne au moins une fonction hydroxyle du polyester est estérifiée par au moins un acide choisi dans le groupe des acides C8-C9-monocarboxyliques isomères, et
    (ii) comme catalyseur (D) au moins un catalyseur contenant du phosphore qui est bloqué par au moins une amine de formule (I)
    Figure imgb0008
     où
    R1 représente un radical hydrocarboné acyclique, aliphatique ou araliphatique comprenant au moins 3 atomes de carbone,
    R2 représente un radical hydrocarboné acyclique, aliphatique ou araliphatique identique à ou différent de R1 et/ou R3 et
    R3 représente hydrogène ou un radical hydrocarboné acyclique, aliphatique ou araliphatique identique à ou différent de R1 et/ou R2.
  2. Mélange de liant selon la revendication 1, caractérisé en ce qu'au moins un des radicaux R1, R2 et R3 représente un radical hydrocarboné aliphatique comprenant 6 à 18 atomes de carbone, de préférence 8 à 14 atomes de carbone et/ou en ce qu'au moins un des radicaux R1, R2 et R3, de préférence au moins 2 des radicaux R1, R2 et R3 et de manière particulièrement préférée les 3 radicaux R1, R2 et R3 représentent des radicaux hydrocarbonés aliphatiques ramifiés et/ou en ce qu'au moins un des radicaux R1, R2 et R3 représente un radical hydrocarboné aliphatique ramifié comprenant 6 à 18 atomes de carbone, de préférence 8 à 14 atomes de carbone.
  3. Mélange de liant selon la revendication 1 ou 2, caractérisé en ce que le catalyseur (D) contenant du phosphore bloqué par amine ou les catalyseurs (D) contenant du phosphore bloqués par amine contien(nen)t au moins une amine tertiaire de formule (I) présentant une longueur du contour de plus de 8 pm (longueur projetée) comme agent de blocage.
  4. Mélange de liant selon l'une quelconque des revendications 1 à 3, caractérisé en ce que le catalyseur (D) contenant du phosphore bloqué par amine ou les catalyseurs (D) contenant du phosphore bloqués par amine est/sont choisi(s) dans le groupe formé par les diesters de l'acide phosphonique et/ou les diesters de l'acide diphosphonique substitués bloqués par amine, les monoesters et/ou les diesters de l'acide phosphorique substitués bloqués par amine, de préférence dans le groupe formé par les diesters de l'acide phosphorique acycliques bloqués par amine et/ou les diesters de l'acide phosphorique cycliques bloqués par amine et de manière particulièrement préférée dans le groupe formé par les esters alkyliques de l'acide phosphorique bloqués par amine et/ou les esters phényliques de l'acide phosphorique bloqués par amine, en particulier les esters phényliques de l'acide phosphorique bloqués par amine et de manière tout particulièrement préférée l'ester phénylique de l'acide phosphorique bloqué par la tris(éthylhexyl)amine.
  5. Mélange de liant selon l'une quelconque des revendications 1 à 4, caractérisé en ce qu'il contient un inhibiteur de cristallisation, si, pour l'amine (I), soit
    (i) R3 représente hydrogène et R1 et R2 représentent des radicaux hydrocarbonés aliphatiques linéaires, soit
    (ii) tous les radicaux R1, R2 et R3 sont des radicaux hydrocarbonés aliphatiques linéaires.
  6. Mélange de liant selon l'une quelconque des revendications 1 à 5, caractérisé en ce qu'il contient au moins un agent de protection contre la lumière à base d'amines stériquement encombrées (HALS) et au moins un absorbant des UV.
  7. Mélange de liant selon l'une quelconque des revendications 1 à 6, caractérisé en ce que le polyester (A) à fonctionnalité hydroxy est un polyester à fonctionnalité hydroxy hyperramifié, dendritique, dans lequel en moyenne au moins une fonction hydroxyle du polyester est estérifiée par au moins un acide choisi dans le groupe des acides C8-C9-monocarboxyliques isomères, de préférence par un acide monocarboxylique saturé, en particulier par l'acide octanoïque ou l'acide isononanoïque, de manière tout particulièrement préférée par l'acide isononanoïque.
  8. Mélange de liant selon l'une quelconque des revendications 1 à 7, caractérisé en ce que le polyester (A) à fonctionnalité hydroxy présente un indice d'OH ≥ 150 mg de KOH/g, de préférence un indice d'hydroxyle > 180 mg de KOH/g, de manière particulièrement préférée de 185-240 mg de KOH/g, à chaque fois déterminé selon la norme DIN 53240, et/ou une fonctionnalité hydroxy (indiquée sur le nombre de groupes hydroxyle libres et estérifiés du polyester) supérieure à 16.
  9. Mélange de liant selon l'une quelconque des revendications 1 à 8, caractérisé en ce que le polyester présente un indice d'acide ≤ 8,0, de préférence de 0-6,0, déterminé selon la norme DIN 53402 et/ou en ce que le polyester présente un poids moléculaire numérique moyen de 1500-4000 g/mole, de préférence de 2000-3500 g/mole, déterminé par CPG avec un témoin de polystyrène dans le THF avec 0,1% en poids d'acide acétique, et/ou en ce que le polyester présente une polydispersité Mw/Mn < 4, de préférence Mw/Mn < 2,5 et de manière particulièrement préférée Mw/Mn ≤ 2,0.
  10. Mélange de liant selon l'une quelconque des revendications 1 à 9, caractérisé en ce qu'il présente une résistance électrique selon la norme DIN 55667 d'au moins 200 kOhm à 25°C et/ou en ce qu'il contient 2,0% en poids à 7,0% en poids, de préférence 2,0% en poids à 5,0% en poids, par rapport aux constituants non volatils du mélange, d'au moins catalyseur (D) contenant du phosphore et de l'azote.
  11. Agent de revêtement contenant un mélange de liant et au moins un composé saturé (B) présentant des groupes isocyanate, qui contient des groupes silanes au moins partiellement hydrolysables, caractérisé en ce qu'il contient un mélange de liant selon l'une quelconque des revendications 1 à 10.
  12. Agent de revêtement selon la revendication 11, caractérisé en ce qu'il contient, comme solvant, de l'acétate de butyle ou un mélange de solvants contenant de l'acétate de butyle, en particulier un mélange de solvants contenant au moins 60% en poids d'acétate de butyle par rapport au poids total du mélange de solvants et/ou en ce que le composé (B) présente entre 2,5 et 97,5% en mole, par rapport à la totalité des unités de structure (III) et (IV), d'au moins une unité de structure de formule (III)

            -N(X-SiR"x(OR')3-x)n(X'-SiR"y(OR')3-y)m     (III)

    où
    R' = hydrogène, alkyle ou cycloalkyle, la chaîne carbonée pouvant être interrompue par des groupes oxygène, soufre ou NRa non adjacents, avec Ra = alkyle, cycloalkyle, aryle ou aralkyle, de préférence R' = éthyle et/ou méthyle,
    X, X' = un radical alkylène linéaire et/ou ramifié ou cycloalkylène, comprenant 1 à 20 atomes de carbone, de préférence X, X' = un radical alkylène comprenant 1 à 4 atomes de carbone,
    R" = alkyle, cycloalkyle, aryle ou aralkyle, où la chaîne carbonée peut être interrompue par des groupes oxygène, soufre ou NRa non adjacents, avec Ra = alkyle, cycloalkyle, aryle ou aralkyle, de préférence R" = un radical alkyle, comprenant en particulier 1 à 6 atomes de carbone,
    n = 0 à 2, m = 0 à 2, m + n = 2 et x, y = 0 à 2,
    et
    entre 2,5 et 97,5% en mole, par rapport à la totalité des unités de structure (III) et (IV), d'au moins une unité de structure de formule (IV)

            -Z- (X-SiR"x(OR')3-x)     (IV),

    où
    Z = -NH-, -NR-,-O-, avec
    R = alkyle, cycloalkyle, aryle ou aralkyle, la chaîne carbonée pouvant être interrompue par des groupes oxygène, soufre ou NRa non adjacents, avec Ra = alkyle, cycloalkyle, aryle ou aralkyle,
    x = 0 à 2 et
    X, R', R" ont la signification indiquée pour la formule (III) .
  13. Procédé de revêtement à plusieurs étapes, caractérisé en ce qu'on applique, sur un substrat le cas échéant revêtu au préalable, une couche de laque de base pigmentée, puis une couche de l'agent de revêtement selon la revendication 11 ou 12.
  14. Utilisation de l'agent de revêtement selon la revendication 11 ou 12 comme laque claire ou utilisation du procédé selon la revendication 13 pour le laquage en série et le laquage de réparation de voitures.
  15. Laquage multicouche conférant un effet et/ou une couleur constitué par au moins une couche de laque de base pigmentée et au moins une couche de laque claire disposée sur celle-ci, caractérisé en ce que la couche de laque claire a été préparée à partir d'un agent de revêtement selon la revendication 11 ou 12.
EP20100744512 2009-09-12 2010-08-03 Mélange à base de liant et agent de revêtement ainsi que revêtements obtenus à partir de ce dernier, présentant une résistance élevée à la rayure, une grande stabilité aux intempéries et de bonnes propriétés optiques Active EP2475698B1 (fr)

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PCT/EP2010/004747 WO2011029502A1 (fr) 2009-09-12 2010-08-03 Mélange à base de liant et agent de revêtement ainsi que revêtements obtenus à partir de ce dernier, présentant une résistance élevée à la rayure, une grande stabilité aux intempéries et de bonnes propriétés optiques

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CN102574970A (zh) 2012-07-11
KR20120092110A (ko) 2012-08-20
WO2011029502A1 (fr) 2011-03-17
US9266995B2 (en) 2016-02-23
US20130052469A1 (en) 2013-02-28
DE102009041380A1 (de) 2011-03-24

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